Proximity effects on semiconducting mineral surfaces II:: Distance dependence of indirect interactions

In a previous study, we described proximity effects on surfaces of the semiconducting minerals galena and pyrite, whereby a chemical reaction at one surface site modifies the reactivity of a remote surface site several Ångstroms or even nanometers away (Becker et al., 2001). The modification of interest does not arise because of a direct “through space” interaction between the two sites, but rather an indirect interaction via the electronic structure of the substrate. Here we investigate the distance and direction dependence of proximity effects using quantum mechanical modeling. The direct and indirect interactions between co-adsorbed oxygen atoms and between adsorbed oxygen atoms and point defects on vacuum-terminated galena (100) surfaces were modeled. Density functional theory cluster and plane wave pseudopotential calculations were used to calculate the modifications to the adsorption energy as a function of separation. Energy-distance plots indicate that the proximity effect energy can become very strong at separations decreasing below about 5 to 6 Å, and persist at increasing separations up to 12 Å in a slowly decaying form. A strong attractive indirect interaction out-competes direct electrostatic repulsion for O-vacancy interactions. An oscillatory asymptotic behavior is found for co-adsorbed O-O indirect interactions, which indicates that the proximity effect energy can vary with surface crystallographic direction. It implies the presence of a strong organizing force on like adatoms that may explain the progressive oxidation of certain sulfide minerals by patchwork growth. These findings begin to pave the way for improved adsorption isotherms and extended surface complexation models that will include the specific influence of semiconductor-type proximity effects.     

The structure and the phyllosilicates (chemistry, crystallinity and texture) of Talas Ala-Tau (Tien Shan, Kyrgyz Republic): comparison with more recent subduction complexes

Geological mapping and structural analysis of the Talas Ala Tau (Tien Shan, Kyrgyz Republic) have revealed a complex structure composed of folds with axial-plane cleavage and thrust faults verging towards the NE. The main structures of the range correspond to minor Tertiary and Carboniferous–Permian deformation superimposed on the main deformation event that took place during the Baikalian orogeny. The pervasive axial-plane cleavage diminishes in penetrativity from the hinterland to the foreland in both the Uzunakhmat and Karagoin sheets. The main thrusts developed phyllonitic shear-related rocks on the hangingwall immediately above the thrust planes. A crystal-chemical study of the phyllosilicates growth during the Baikalian deformation event along a cross-section revealed changes in the crystallinity, composition and lattice parameters of them. The phyllosilicates present in the Talas Ala Tau rocks were crystallized in very low-grade metamorphic conditions, that is below 300 °C, as indicated by their Kübler Index (KI), which decreases from SW towards the NE. Detailed TEM study of the phyllosilicates reveals a clear textural difference at the lattice level between samples with higher or lower KI parameters. There is also a clear difference in crystal-chemical parameters (KI and b) and composition between the phyllosilicates growth in relation to the axial-plane cleavage and the ones belonging to the thrust-related phyllonites. The first ones are more affected by the ferrimuscovitic vector than the phyllosilicates of phyllonites, closer to the theoretical phengitic component. Huge ranges of values of phengitic content of micas at sample level are interpreted as the result of a decompression path from at least 8 kbar. We propose a subduction geodynamic environment for the regional deformation and the origin of the phyllosilicates, as they are similar to those obtained in more recent accretionary complexes.     

Stable isotope laser spectrometer for exploration of Mars

On Earth, measurements of the ratios of stable carbon isotopes have provided much information about geological and biological processes. For example, fractionation of carbon occurs in biotic processes and the retention of a distinctive 2-4% contrast in 13C/12C between organic carbon and carbonates in rocks as old as 3.8 billion years constitutes some of the firmest evidence for the antiquity of life on the Earth. We have developed a prototype tunable diode Laser spectrometer which demonstrates the feasibility of making accurate in situ isotopic ratio measurements on Mars. This miniaturized instrument, with an optical path length of 10 cm, should be capable of making accurate 13C/12C and 15N/14N measurements. Gas samples for measurement are to be produced by pyrolysis using soil samples as small as 50 mg. Measurements of 13C/12C, 18O/16O and 15N/14N have been made to a precision of better than 0.1% and various other isotopes are feasible. This laser technique, which relies on the extremely narrow emission linewidth of tunable diode lasers (<0.001 cm(-1)) has favorable features in comparison to mass spectrometry, the standard method of accurate isotopic ratio measurement. The miniature instrument could be ready to deploy on the 2003 or other Mars lander missions.     

Does application of the Rosiwal Principle to lunar soils require that concentrations of solar-wind-implanted species be grain-size independent?

A reconsideration of the application of the Rosiwal Principle to lunar soils indicates a flaw in arguments put forth previously by Criswell. Specifically, by introducing a boundary condition which must exist at the lunar surface, it is shown that concentrations of solar-wind-implanted species showing a dependence on grain size may be able to develop in soils at concentration levels below those required for saturation of grain surfaces. As a result, observed grain-size-dependent concentrations of solar-wind species in lunar soils do not necessarily require the exposure time scales or solar-wind fluxes deduced from the arguments of Criswell.     

The state and the land question of the frontier — a geopolitical perspective

This paper analyzes the role played by the state in the expansion of the frontier from a geopolitical viewpoint. In this regard, emphasis will be placed on the question of access to the land as related to the work force mobility, a vital aspect for understanding geopolitical attitudes. Land-opening and migration policies will be considered in association with the implicit strategy of the state, as well as in its consequences for the expansion of the frontier in the E Amazon basin. A return to geopolitical analysis of the space seems opportune at a time when new policies of space management and territorial control are becoming more evident.     

Winde und turbulente Luftströmungen in der Ionosphäre

Zusammenfassung Siehe Abschnitt IV.

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Summary Occurrence of predominantly horizontal linear air currents in the ionosphere could be verified by direct and indirect electrical observations. The maximum of frequency of the measured wind velocities lies, within the range of 80 and 120 km altitude, at 60 m/sec and within theF-layer (200 to 350 km altitude) at 100 m/sec. The measured wind velocities do not show a uniform pattern. The standard deviation of the observations reaching several 100 per cent makes it probable that wind direction and speed depend on the hour of day and the season as well as on the geographical latitude and altitude. Considering particularly theF-layer the velocity of propagation of the deviation centers was found to be proportional to the earth-magnetic characteristic number. The extention of these deviation centers, however, does not depend on the intensity of the earth-magnetic disturbance and is nearly constant also in other respects. These more or less linear air currents are combined with a more or less turbulent movement. The direct and indirect observations verify this for the range between 80 and 100 km altitude; knowledge on the respective conditions in theF-layer, however, could not be obtained by them. The root of the average velocity square of all velocity components in the direction of the observations amounts to approximately 2 m/sec. The occurrence of solar and lunar tides in the range of theE-layer with a velocity amplitude of 35 and 25 m/sec respectively can be considered as a indisputable fact, whereas for theF-layer there exist too few investigations as yet.

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Résumé La présence de courants d'air essentiellement horizontaux dans l'ionosphère a été prouvée par des observations visuelles directes et électriques indirectes. Le maximum de fréquence des vitesses de vent mesurées se trouve dans la couche comprise entre 80 et 120 km, où elles atteignent 60 m/s, ainsi qu'au niveau de la coucheF (200–350 km) avec 100 m/s. Les directions observées ne fournissent pas d'image simple; la dispersion des mesures conduit à penser que les azimuts et les vitesses dépendent du moment du jour et de la saison, comme de la latitude et de l'altitude. En ce qui concerne la coucheF en particulier, il apparaît que la vitesse de déplacement des centres de dispersion est proportionnelle au nombre caractéristique géomagnétique. La grandeur de ces centres est toutefois indépendante de l'intensité de la perturbation géomagnétique et reste à peu près constante.A ces courants ionosphériques plus ou moins linéaires se superpose un courant d'air plus ou moins turbulent; les observations directes et indirectes vérifient ce fait pour la couche comprise entre 80 et 120 km, mais elles ne peuvent rien dire à ce sujet en ce qui concerne la coucheF. La racine carrée du carré moyen des vitesses de toutes les composantes de vitesse dans la direction d'observation est égale à 2 m/s environ.L'existence de marées solaires et lunaires dans la coucheE avec une amplitude des vitesses de respectivement 35 et 25 m/s peut être considérée comme assurée; les recherches analogues concernant la coucheF sont encore trop peu nombreuses.

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Mit 6 Textabbildungen.     

An attempt to define a “neotectonic period” for central and northern Europe

The neotectonic period is the youngest period of tectonic evolution and extends up to the present. The beginning of the neotectonic period during the Cenozoic may be regarded as having begun when characteristic changes in the tectonic evolution of a region of interest have occurred for the last time. Changes in the different tectonic facets, which characterize the evolution of a region, need not be simultaneous, and hence the times of the last change may differ between facets. This leads to the definition of a transitional time interval wherein elements of both the palaeotectonic and neotectonic period are present. The length of this transitional time interval depends on the regional geological evolution. Where a broad transitional time interval exists, the beginning of the neotectonic period may be defined by the earliest time marker by when most of the characteristic changes of the tectonic evolution of the region had occurred.In defining the neotectonic period in central and northern Europe, data on the evolution of the northern Mid-Atlantic ridge and the northern Mediterranean convergence zone, inversion tectonics in northern and central Europe, rifting, regional subsidence and uplift, and the tectonic stress field as well as the evolution of the calcalkaline and alkaline volcanism in central Europe have been taken into account. The chronological evolution of these characteristics for the Cenozoic have been analysed with a view to identifying the advent of the neotectonic period. The transition from the end of the palaeotectonic period to the beginning of the neotectonic period extends from the middle early Miocene to the Miocene-Pliocene boundary. The earliest time by when most of the characteristic changes in the tectonic evolution of northern and central Europe had occurred is the early late Miocene. Thus, the neotectonic period can be considered to have begun at approximately 10 Ma before present.     

Temperature-jump induced cation exchange kinetics in (Co<Subscript>0.1</Subscript>Mg<Subscript>0.9</Subscript>)<Subscript>2</Subscript>SiO<Subscript>4</Subscript> olivine: an in situ optical spectroscopic study

In the olivine crystal structure, cations are distributed over two inequivalent octahedral sites, M1 and M2. Kinetics of cation exchange between the two octahedral sites in (Co_0.1Mg_0.9)₂SiO₄ single crystal have been studied in the temperature range from 600 to 800°C by monitoring the time evolution of the absorbance of Co²⁺ ions in M1 or M2 sites using optical spectroscopy after rapid temperature jumps. It was found from such temperature-jump induced relaxation experiments that with increasing temperature the absorbance of Co²⁺ ions in the M1 site decreases while that in the M2 site increases. This indicates a tendency of Co²⁺ cations to populate the M2 site with increasing temperatures and vice versa. The experimental relaxation data can be modeled using a triple exponential equation based on theoretical analysis. Activation energies of 221 ± 4 and 213 ± 10 kJ/mol were derived from relaxation experiments on the M2 site and M1 site, respectively, for the cation exchange processes in (Co_0.1Mg_0.9)₂SiO₄ olivine. Implications for cation diffusion at low temperatures are discussed.